Phys Chem Minerals DOI 10.

1007/s00269-009-0323-1

ORIGINAL PAPER

Modelling of Al impurity in perovskite and ilmenite structures of MgSiO3

Arvids Stashans Leonardo Eras Gaston Chamba

Received: 22 January 2009 / Accepted: 20 July 2009 Springer-Verlag 2009

Abstract A methodology based on the HartreeFock theory is used to study pure MgSiO3 crystals as well as Al doping in perovskite and ilmenite modications of this mineral. Atomic displacements in the neighbourhood of the defect are obtained for cases when the Al substitutes for either Mg or Si host atoms. The atomic relaxation is due to the changes produced upon the chemical bonding within the defective region and in some occasions obeys the Coulomb electrostatic interaction. Band structure properties are briey revised for the pure and doped minerals. The occurrence of Al-bound hole polaron is predicted in the ilmenite mineral. The results of output are compared to the available reports on the same subject in both experimental and theoretical elds of the investigation. Keywords Magnesium silicate Aluminium doping Structure Electronic properties HartreeFock method

Introduction The Earths mantle, a complex mixture of silicates and oxides, accounts for about half of the total Earth mass. The mineralogical composition of the mantle simplies with
A. Stashans (&) L. Eras G. Chamba Grupo de Fisicoqumica de Materiales, Instituto de Qumica Aplicada, Universidad Tecnica Particular de Loja, Apartado 11-01-608, Loja, Ecuador e-mail: arvids@utpl.edu.ec G. Chamba e-mail: grchamba@utpl.edu.ec G. Chamba Escuela de Electronica y Telecomunicaciones, Universidad Tecnica Particular de Loja, Apartado 11-01-608, Loja, Ecuador

increasing pressure and temperature, and the different discontinuities identied by seismic analysis usually correspond to mineral phase transformations. The 660 km seismic discontinuity marks the separation between the Earths upper and lower mantle, the region in the Earth extending from about 660 km to approximately 2900 km depth. It is widely accepted that magnesium silicate (MgSiO3) makes up to 70 vol.% of the material in the lower mantle. Actually over 40% of the entire planet is composed of MgSiO3 mineral. Because of the high pressures and temperatures involved, it is very difcult to carry out experiments to study the properties of this important material. Hence, the elds of computational physics and computational chemistry are active to simulate the behaviour and properties of the material that make up our planets interior. In recent years, a number of theoretical reports have been published on MgSiO3 material. One of the main tools to simulate this material is the molecular dynamics technique which is a classical, atomistic approach based upon integrating Newtons laws of motion for an ensemble of particles which interact via interatomic forces. This methodology has been applied to study high pressure thermoelastic properties of MgSiO3 perovskite over a wide range in PT space (Patel et al. 1996; Liu et al. 2007), structure and physical properties of MgSiO3 (Matsui 1988; Carrier et al. 2007), equations of state (Liu et al. 2006a, b), highpressure phase transitions in MgSiO3 orthoenstatite (Jahn 2008), the melting curve (Liu et al. 2006a, b), modelling of dislocations (Carrez et al. 2007) etc. Meantime, an increase in utilization of different methods based on the quantum mechanical background in order to investigate these crystals has been notable. Few examples include the study of different MgSiO3 structures from the point of view of the HartreeFock methodology (DArco et al. 1993; DArco

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et al. 1994) and a huge amount of research based on the density functional theory (DFT) approximations like structural instabilities in MgSiO3 (Warren and Ackland 1996), phonon dispersions as a function of pressure up to 150 GPa (Karki et al. 2000), bio-compatible piezoelectricity (Uetsuji et al. 2005), potassium partitioning between Fe- and Al-bearing MgSiO3 minerals (Lee et al. 2009) and others. In parallel to theoretical investigations there are a number of important experimental works done in the eld. Only few examples of recent years publications include growth of large MgSiO3 perovskite single crystals (Shatskiy et al. 2007), X-ray diffraction study of polymorphism of MgSiO3 (Foster 2006), synthesis of MgSiO3 at high temperatures and pressure (Mosenfelder et al. 2009), as well as research of Al impurity inuence upon compressibility (Saikia et al. 2009), sintering and crystallization (Goel et al. 2008), as well as the equation of state of MgSiO3 (Andrault et al. 2007). Although intensively studied for a long time as stated above, a lot of aspects of mineral chemistry and physics of MgSiO3 are still debated. In particular, it is still unclear to predict the principal effects produced by different impurity doping in various phases of the MgSiO3 mineral. The Al impurity presence is of special interest since the MgSiO3 is the major carrier of Al. In general, an impurity atom may enhance certain properties of a given material, which could be further used in different applications. Here we would like to accent that many important properties of any material or mineral are due to the microscopic origin. Quantum mechanics is the only reliable tool to describe any physical system at the microscopic scale. Notable amongst the principles of quantum mechanics are both a dual wave-like and particle-like behaviour of matter, and prediction of probabilities in situations where classical physics predicts certainties. These leads to classically impossible situations like the fractional charges on atoms and the fractional electron populations of the chemical bonding. Despite the fact that geosciences usually deal with systems big enough to ensure that laws of classical mechanics are at work it is good not to forget that many macroscopic properties of minerals might be direct consequences of quantum behaviour of some parts of these minerals. Bearing that in mind we try to discover effects produced upon the MgSiO3 minerals by a particular impurity. We are aware that in the nature, e.g. in the lower mantle of the Earth there are a number of impurities and generally point defects present at the same time which make this system just like it appears. Perhaps, from the point of view of geosciences it would be more logical to model different impurities at the same time maintaining thus also the charge balance. Nevertheless, we would never know what kind of effects is produced by a particular impurity. On the other hand, the careful description of a

given physical system taking into account precisely the details on crystal spatial structure, chemical bonding and correct treatment of the impurity introduction is very important. This means that correctly picked out physical model even with less precise mathematical formalism might yield a signicant improvement in our understanding on systems like MgSiO3. This is the reason why we chose to exploit a computer code based on the semi-empirical HartreeFock methodology adjusted for defect studies in periodic systems (crystals).

Brief computational details Modern physics relies heavily on the concepts of classical solid state physics with its emphasis on ideal innite crystals and perfect symmetries. Real minerals are not pure crystals; they are materials containing a number of defects and lattice imperfections. Basically, the properties of materials are due to these defects and imperfections. Therefore, the reliability of physical model rather than precision of mathematical equations should be emphasized if one needs to investigate real minerals existing in the nature. With this in mind, we have chosen to use the semiempirical quantum-chemical computer code based on the HartreeFock theory. The software rstly developed for study of ionic crystals and called CLUSTERD (Stefanovich et al. 1990) has been later parametrized to be able to make a research on complex systems with covalent or semiioniccovalent chemical bonding and bearing different point defects, i.e. systems resembling real minerals. The basic idea of approach has been proposed in the review article (Stashans 2004), where also the importance of physical model is discussed in detail. Here we shall only note that the method calculates both the electronic band structure and the total energy of a given crystal via molecular orbital as a linear combination of atomic orbitals (AOs). The method uses periodically repeated supercells and permits one to treat the inherent complexity of systems yielding valuable information on electronic structure and predicting geometries of defects and impurities therein. In our particular case, we have used 160-atom supercell being constructed as 8-times extension (2 9 2 9 2 symmetric extension) of 20-atom primitive unit cell of the orthorhombic MgSiO3 perovskite structure. In case of the trigonal MgSiO3 ilmenite mineral we exploited 120-atom supercell which was set up by extending 4-times (2 9 2 9 1 symmetric extension) 30-atom primitive unit cell. The atomic parametrization for both minerals included the reproduction of main features of the electronic band structure and geometry, i.e. lattice parameters. The normal ambient condition of temperature and pressure was

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considered for the reproduction of mineral structures. Actually, we based our search for the best numerical values of the atomic parameters on already available data (Stefanovich et al. 1990) and adjusted these gures to our particular case. As it is shown in Table 1 our numerical parameters allowed reproducing with a high precision the spatial structures of both minerals practically matching the values of lattice parameters to the experimental X-ray diffraction data. Due to the lack of photoconductivity experiments on both MgSiO3 perovskite and ilmenite minerals our calculated band-gap magnitudes cannot be compared to the experimental results. However, our outputs for band-gap widths as well as charges on atoms agree reasonably well with some ab initio studies as it is indicated in Table 1. Thus obtained numerical parameters for the Mg, Si and O atoms are given in Tables 2, 3. The parametrization of Al atom has been carried out by one of us (A.S.) before (Jacobs et al. 1992) within the corundum a-Al2O3 crystal. It is worth mentioning that our method is especially reliable for the defect-doping studies in crystals and recent investigations (Stashans et al. 2008, Stashans and Vidal 2008, Rivera and Stashans 2008) prove that. That is because in case of oxides, e.g. MgSiO3 crystals, an important role has been played by the electron exchange interaction. This reciprocal action between the valence electrons is not reproduced adequately in different cluster models. Basically the exchange interaction is treated well within the cluster region while it is omitted in the case
Table 1 Main properties of pure MgSiO3 perovskite and ilmenite minerals obtained within our research in comparison to another studies Perovskite MgSiO3 Lattice parameters a, b and c (A) Present Ab initio Experimenta study calculation 4.78 4.93 6.90 Band gap width (eV) Charges on atoms for Mg, Si and O (e) 6.5 1.83 2.80 -1.54 Ilmenite MgSiO3 Lattice parameters a and c (A) Band gap width (eV) Charges on atoms for Mg, Si and O (e) Present study 4.73 13.56 4.9 1.75 2.49 -1.46
a

Table 2 Numerical parameters used to simulate MgSiO3 structures Atom Mg Si O Al AO 3s 2p 3s 3p 2s 2p 3s 3p f (a.u.) 1.40 2.55 1.54 1.54 2.27 1.86 1.60 1.50 Eneg (eV) 16.00 43.00 7.40 -0.70 4.50 -12.60 17.15 12.50 P0 (e) 0.15 2.00 1.00 1.00 1.974 1.96 0.71 0.39 b (eV) -1.10 -3.00 -8.00 -8.00 -16.00 -16.00 -1.50 -1.50

Table 3 Two centre semi-empirical parameters alB (a.u.-1) where l[A Atom A Atom B = Mg Mg Si O Al 0.25 0.10 0.317 0.10 Atom B = Si 0.00 0.00 0.31 0.00 Atom B=O 0.05 0.05 0.15 0.10 Atom B = Al 0.00 0.00 0.30 0.00

4.786b 4.913 6.896 5.95c 1.565d 2.329 -1.298 Ab initio calculation 4.713b 13.454

4.7787 4.931 6.899

between the cluster region and the residual part of the crystal. The periodic supercell model used in the present study stands out for a very careful treatment of exchange interaction (Lunell et al. 1997, Stashans 2004) with only approximation being the introduction of the so-called cutoff function. Since instead of rapidly vanishing Gauss functions our computer code uses Slater-type AOs the latter approximation does not have any considerable inuence on the computational results. The articial mutual defectdefect interaction existing in any periodic model is overcome by the selection of adequately large supercells to avoid such a counterfeit effect. Thereby our method allows one to study a single point defect within a highly reliable periodic model.

Results
Experimente 4.7284 13.5591

Pure perovskite and ilmenite structures The perovskite MgSiO3 has the space group Pbnm which belongs to the orthorhombic system and deviates signicantly from the ideal cubic-perovskite structure through the tilting of the SiO6 octahedra and the large distortion of the MgO12 dodecahedron. The geometry optimization of pure MgSiO3 perovskite lattice was part of the parametrization procedure. It was found that the Si atom is located in the centre of the SiO6 octahedron and thus is the centre of symmetry. The obtained SiO distances in the SiO6

Horiuchi et al. 1987, DArco et al. 1994, cKarki and Khanduja 2006, dMatsui 1988, eHoriuchi et al. 1982

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Phys Chem Minerals Fig. 1 Calculated DOS for the MgSiO3 perovskite structure. The lower VB is mainly O 2s in nature; the upper VB is composed predominantly of the O 2p AOs while the bottom of the CB is formed by the Si 3s states with a notable admixture of the Mg 3s AOs. The narrow sub-band of the Mg 2p states nds itself between the lower VB and the upper VB. The estimated band-gap value is about 6.5 eV with vertical line denoting the energy reference, i.e. the HOMO level

octahedron ranges from 1.78 to 1.80 A. The position of the Mg atom deviates from the centre of the MgO12 polyhedron which results in a wide range of the MgO distances. According to our geometry optimization these distances vary from approximately 2.01 to 3.12 A. The optimized lattices parameters for this structure were found to be equal to a = 4.78, b = 4.93 and c = 6.90 A. As stated above these gures practically match the experimental data obtained by a single crystal X-ray diffraction study (Horiuchi et al. 1987). The total density of states (DOS) obtained by the CLUSTERD computer code is plotted in Fig. 1. The lower valence band (VB) is composed practically only of the O 2s states. The next lled energy band is exclusively Mg 2p in nature. This sub-band is very narrow. Above the Mg 2p sub-band, the wide upper VB is situated. According to our modelling this band is composed predominantly of the O 2p AOs. We can mention, however, that some admixture of the Si 3s states is also found within this energy range. The computed conduction band (CB) consists of two parts. The bottom of the CB is composed prevailingly of the Si 3s AOs with a strong admixture of the Mg 3s states. The second peak of the CB having higher energies is due to the Si 3p AOs. The calculated band-gap value as a difference between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) within the CLUSTERD code is found to be equal to 6.5 eV. This gure is close to the band-gap value of 5.95 eV estimated by the DFT-based PWscf code (Karki and Khanduja 2006). Here we should point out to the fact that ab initio methods based on the HartreeFock approach normally overestimate the band-gap value due to the omission of correlation effects. On the other hand, the DFT-based computer codes underestimate it due to the

local density approximation. The CLUSTERD computer code does account for the short-range correlation effects through the atomic parametrization (Jacobs et al. 1992) omitting only the long-range correlation effects. This is the reason why our computed band-gap value is so close to the DFT-yielded magnitude. This nding also implies a considerable ionic character in the chemical bonding between the atoms in MgSiO3 perovskite mineral. This inference is additionally supported by the acquired charges on atoms using the Lowdin population method (Lowdin 1950): they are 1.83 e, 2.80 e and nally -1.54 e for the Mg, Si and O atoms, respectively. The ilmenite MgSiO3 mineral has the space group R 3 which belongs to the trigonal system. Its structure might be obtained by replacing Mg for Fe and Si for Ti in the wellknown ilmenite FeTiO3 compound. This is a structure which perhaps is best considered as a slightly distorted hexagonal close-packing of the O atoms with smaller metallic atoms (Mg and Si) lying in some of the interstices. The arrangement of O atoms in this system has a wide range of OO distances (2.333.08 A). The SiO distances in SiO6 octahedra lie in between 1.77 and 1.83 A. The MgO6 octahedra are rather compressed with the MgO distances ranging from 1.99 to 2.16 A. The computed lattice parameters of the hexamolecular cell referred to hex agonal axes are found to be equal to a = 4.73 A and c = 13.56 A, which coincide with the corresponding X-ray diffraction measurements for the MgSiO3 ilmenite-type crystals (Horiuchi et al. 1982). The DOS pattern of pure MgSiO3 ilmenite mineral is given in Fig. 2. The lower VB is composed practically only of the O 2s states and has two peaks. The upper VB is structured by the O 2p AOs with some admixture of the Si 3s states. There is a narrow sub-band of the Mg 2p states

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Phys Chem Minerals Fig. 2 Calculated DOS for the MgSiO3 ilmenite structure with the band compositions being very similar to those of the MgSiO3 perovskite case. However, the obtained band-gap value is found to be close to 4.9 eV implying more covalent character of the chemical bonding in this mineral. The vertical line denotes the energy reference, i.e. the HOMO level

sandwiched between the lower and the upper VBs. The bottom of the CB is mainly Si 3s in nature smoothly transferring into the Mg 3s states at higher energies. Finally, the top of the CB is due to the Si 3p states. The computed magnitude of band-gap width as a difference of the HOMO and the LUMO states is found to be equal to 4.9 eV implying that pure ilmenite structure has somewhat more considerable contribution of the covalent character into its chemical bonding compared to that of the perovskite MgSiO3 mineral. This is testied supplementary by the obtained charges on atoms being equal to 1.75 e, 2.49 e and -1.46 e for the Mg, Si and O atoms, respectively. Al doping in MgSiO3 perovskite mineral Substitution by Al atom impurity can occur in both Mgand Si-sub-lattices of the MgSiO3 perovskite mineral. In case of the Al ? Mg substitution we have the so-called donor impurity doping whereas the Al ? Si replacement is the acceptor-type doping. Both doping kinds might occur in the nature, and therefore we have considered both of them. When the Al impurity substitutes for the host Mg atom, the following atomic displacements in the vicinity of defect are found. The seven impurity-nearest O atoms move towards the defect (Table 4 and Fig. 3) by magnitudes ranging from 0.08 to 0.24 A while one O atom, O(7), tends to displace itself away with respect to the Al atom by about 0.04 A. The values of atomic relaxation depend on the initial distance from a particular atom till the Al impurity and thus the strength of the perturbation, which the defect produces on its surroundings. The two Al-neighbouring Si atoms also move towards the defect due to the electrostatic reasons. The charge on Al atom, 1.61 e, is smaller compared

Table 4 Obtained charges on atoms and displacements of the defectnearest atoms when an Al impurity replaces for one of the Mg atoms in the MgSiO3 perovskite mineral Atom Charge in pure crystal Charge in doped (e) crystal (e) Si(1) Si(2) O(1) O(2) O(3) O(4) O(5) O(6) O(7) O(8) 2.80 2.80 -1.54 -1.54 -1.54 -1.54 -1.54 -1.54 -1.54 -1.54 2.99 2.96 -1.55 -1.59 -1.56 -1.55 -1.54 -1.54 -1.57 -1.54 Displacement (A) -0.04 -0.08 -0.16 -0.16 -0.24 -0.24 -0.24 -0.08 0.04 -0.08

Negative atomic shifts stand for the defect-inward movements. The atomic numeration corresponds to the one shown in Fig. 3

to the corresponding number on the host Mg atom, 1.83 e, thus yielding the reduction in the Coulomb electrostatic repulsion between these two Si atoms and the newly introduced Al impurity. Despite the fact that there is one extra electron in the system originating from the donortype doping we observe some augmentation in the magnitude of charges on atoms (see Table 4). This implies more ionic nature in the chemical bonding between the atoms in the defective region. We also notice a local, oneelectron energy level in the gap between the upper VB and the CB situated about 2.9 eV above the top of the upper VB, i.e. approximately in the middle of the band-gap. The wave-function describing this energy level is mainly due to the Al 3s AO with some admixture of the O 2p states belonging to the defect-surrounding O atoms.

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Fig. 3 A schematic diagram of atomic relaxation obtained due to the Al doping in Mg-sublattice of the 160-atom MgSiO3 perovskite mineral supercell. The atoms placed in the vicinity of defect are indicated only. The computed atomic displacements shown by pointers are found to be mainly towards the impurity atom

Fig. 4 A schematic diagram of atomic relaxation computed because of the Al doping in Si-sublattice of the 160-atom MgSiO3 perovskite mineral supercell. The defect-nearest atoms receiving the major perturbation are shown. The obtained atomic displacements in the defective region are towards the impurity atom

Table 5 Obtained charges on atoms and displacements of the defectnearest atoms when an Al impurity replaces for one of the Si atoms in the MgSiO3 perovskite mineral Atom Charge in pure crystal Charge in doped (e) crystal (e) Mg(1) Mg(2) Mg(3) Mg(4) O(1) O(2) O(3) O(4) 1.83 1.83 1.83 1.83 -1.54 -1.54 -1.54 -1.54 1.85 1.85 1.85 1.85 -1.33 -1.52 -1.52 -1.52 Displacement (A) -0.01 -0.01 -0.02 -0.01 -0.09 -0.03 -0.02 -0.03

substitution reported above. In our mind, this is due to the fact that Al produces smaller perturbation upon its vicinity since it can accommodate itself with more facility in the Si-sub-lattice. No local band-gap energy level due to the impurity presence is found in this particular case. Al doping in MgSiO3 ilmenite mineral Al doping in the MgSiO3 ilmenite mineral also was done by considering both Mg- and Si-sub-lattices. The Al ? Mg replacement can be considered as a donor-type doping since one extra valence electron is added to the system. The computed atomic displacements due to the defect-enforced perturbation are depicted in Table 6 and Fig. 5. As one can notice the atomic shifts are mainly away with respect to the defect position. Thus the obtained pattern is quite different from the one found in the Al ? Mg substitution in the case of the MgSiO3 perovskite mineral. Without going into details we reckon that the origin of such a contrast is the charge on the Al impurity being equal to only 0.89 e. The latter might be responsible likewise for the fact that no local energy level is observed in the band gap of the material with contributions of the Al 3s states falling well deep into the upper VB of the mineral. The effects on ilmenite structure produced by the Al doping in the Si-sublattice are presented in Table 7 and Fig. 6. This acceptor-type doping leads to the atomic charge of 1.54 e on the Al impurity which is considerably smaller as the corresponding value on the host Si atom, 2.49 e, in the pure ilmenite structure. Despite the main tendency of the defect-nearest atoms to move outwards the Al impurity, some of them rearrange themselves towards

Negative atomic shifts stand for the defect-inward movements. The atomic numeration corresponds to the one given in Fig. 4

In the case of the Al ? Si replacement we observe a notable change in the charges of atoms, which are located close to the impurity. The charge on Al atom is found to be equal to 1.99 e while the charge of the host Si atom, for which the impurity substitutes, is around 2.80 e. Thus the performed acceptor-type doping creates rather strong electron population depletion leading to the increase of positive charges on Mg and Si atoms accompanied by the reduction of the magnitude of the negative charges on the O atoms (Table 5). The computed atomic relaxation (Table 5 and Fig. 4) is again towards the impurity atom being considerably smaller as for the case of the Al ? Mg

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Phys Chem Minerals Table 6 Obtained charges on atoms and displacements of the defectneighbouring atoms if an Al impurity replaces for one of the Mg atoms in the MgSiO3 ilmenite mineral Atom Mg Si(1) Si(2) O(1) O(2) O(3) O(4) O(5) O(6) O(7) Charge in pure crystal (e) 1.75 2.49 2.49 -1.41 -1.41 -1.41 -1.46 -1.46 -1.38 -1.38 Charge in doped crystal (e) 1.75 2.54 2.48 -1.50 -1.25 -1.31 -1.54 -1.41 -1.39 -1.43 Displacement (A) 0.08 -0.08 -0.16 0.41 0.41 0.16 0.24 0.04 -0.08 0.33

Negative atomic shifts stand for the defect-inward relaxation. The atomic numeration coincides with the one shown in Fig. 5

Fig. 5 A schematic diagram of atomic relaxation obtained due to the Al doping in Mg-sublattice of the 120-atom MgSiO3 ilmenite mineral supercell. The defect-neighbouring atoms are indicated only. The computed atomic displacements with respect to the defect are shown by pointers

the defect. Those are predominantly defect-neighbouring O atoms which also suffer a determined reduction in their negative atomic charges. In general, the obtained pattern testies further fostering of already strong covalent character of the chemical bonding in the ilmenite mineral.

Discussion Quantum chemical investigation of the MgSiO3 perovskitetype mineral suggests that the Al track element might have a signicant inuence on chemistry of the deep Earths mantle possessing mainly this mineral. The major part of the chemical bonding originates from the ionic interaction

within the material and the Al introduction maintains this pattern. The acquired atomic displacements indicate some shortening of chemical bonds in the defective region especially if the case of Al ? Mg replacement is taken into account. This is in accordance with the performed Rietveld analysis (Kojitani et al. 2007) testifying a notable decrease in the MgO distances when the Al atom goes to the Mg-sublattice. In our mind, the defect-inward atomic shifts are due to the smaller ionic radius of Al3?, 0.535 A, 2? compared to the corresponding magnitude for the Mg , 0.72 A. The defect inclusion creates some extra space within the crystalline lattice permitting atoms to move towards the Al impurity. Generally, there is some tilting of the SiO6 octahedra. The defect-inward movements of Si atoms can be interpreted by the fact that despite high ionicity of the material there is a notable covalent admixture just in the SiO chemical bonding, which can be seen from the bond populations. Thereby the Si atoms tend to follow their neighbouring O atoms in the relaxation pattern. The observed local one-electron energy level in the middle of the band-gap being composed of the Al 3s AO might produce some changes into the absorption spectra of this mineral and hopefully our results would encourage experimental investigations in this area. The perturbation produced by the Al ? Si doping is rather small yielding slighter atomic shifts. This implies that the MgAlxSi1-xO3 system is more stable than the AlMg1-xSiO3 compound and the Al defect would better prefer to substitute into the Si-sublattice. This is in agreement with the experimental X-ray diffraction study (Vanpeteghem et al. 2006) and recently performed DFT computations (Brodholt 2000). The MgSiO3 ilmenite-type crystal has partly ionic covalent chemical bonding with a somewhat stronger ionic contribution. The performed Al doping in this mineral enhances furthermore the importance of covalent character in the chemical bonding. The Al ? Mg donor-type substitution creates a drawing where electron population is partially redistributed from the ions towards the chemical bonds as it follows from our carried out Lowdin population dissection. This leads to the enlargement of especially AlO bonds and the respective outward motions of the defect-nearest O atoms. In overall, the majority of atoms situated in the defective region experiences Al-outward movements except a pair of Si atoms. These two atoms shift themselves towards the defect obviously due to the reduction in mutual Coulomb repulsion force (remember that the atomic charge on the Al impurity is 0.89 e only). The Al ? Si doping yields somewhat different picture in atomic shifts although the chemical bonding has the same tendency to become slightly more covalent. The main reason for almost opposite atomic movements originates from the fact that this acceptor-type doping facilitates the occurring of Al-bound hole, the so-called hole polaron.

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Phys Chem Minerals Table 7 Obtained charges on atoms and displacements of the defectneighbouring atoms if an Al impurity replaces for one of the Si atoms in the MgSiO3 ilmenite mineral Atom Mg(1) Mg(2) Mg(3) Si(1) Si(2) Si(3) O(1) O(2) O(3) O(4) O(5) O(6) O(7) O(8) O(9) O(10) O(11) Charge in pure crystal (e) 1.75 1.75 1.75 2.49 2.49 2.49 -1.41 -1.41 -1.41 -1.46 -1.46 -1.46 -1.46 -1.46 -1.38 -1.38 -1.38 Charge in doped crystal (e) 1.75 1.78 1.76 2.29 2.58 2.30 -0.96 -1.42 -1.16 -1.45 -1.45 -1.30 -1.27 -1.45 -1.08 -1.21 -1.35 Displacement (A) -0.16 0.41 -0.08 0.16 0.08 0.08 -0.08 -0.24 -0.24 0.04 0.04 -0.33 0.08 0.04 -0.24 -0.41 0.16

Negative atomic shifts stand for the defect-inward relaxation. The atomic numeration coincides with the one shown in Fig. 6 Fig. 6 A schematic diagram of atomic relaxation calculated due to the Al doping in Si-sublattice of the 120-atom MgSiO3 ilmenite mineral supercell. The defect-neighbouring atoms are indicated only. The computed atomic displacements with respect to the impurity atom are shown by pointers. The formation of Al-bound hole polaron taking place on the O(1), O(3) and O(9) atoms forces these three atoms to move towards the Al impurity and also towards each other

This quasi-particle localizes mainly on three O atoms: O(1), O(3) and O(9) atoms (Fig. 6). The process of hole polaron creation requires that the previously mentioned three O atoms move not only towards the Al impurity but also towards each other. The spatial and electronic congurations of the Al-bound hole polaron is similar to those encountered before in another oxides (Pinto and Stashans 2000; Stashans 2001). The occurrence of Al-bound hole polaron provokes an electron population redistribution in the Al-surrounding region to a considerable extent and the rest of the atoms in the defective region changes their positions according to this phenomenon. In general, the obtained predominantly opposite atomic movements in ilmenite, especially those of the O atoms for these two types of doping, Al ? Mg and Al ? Si substitutions, agree very well with the data provided by the DFT-assisted study on the inuence of Al content on the bulk modulus, which has an opposite sign for the discussed two types of doping (Panero et al. 2006).

Conclusions The CLUSTERD computer code created on the basis of the HartreeFock theory has been exploited to investigate perovskite and ilmenite structures of the MgSiO3 mineral

as well as Al atom doping therein. The obtained outcomes on pure minerals and their structures argue for mainly ionic chemical bonding in the perovskite modication whilst the bonding in ilmenite resembles to be partly ioniccovalent. The main conclusion which can be drawn from results of the accomplished doping in the perovskite crystal is that such kind of perturbation produces small impact on the elastic properties of the mineral due to rather scanty atomic displacements obtained when the Al impurity substitutes for the host Si atom. This particular doping is found to be more preferable as another feasible case of the Al replacement in Mg-sublattice in agreement with a number of experimental measurements. The carried out Al doping in the ilmenite mineral leads to interesting nding of the Al-bound hole polaron, a quasiparticle, which occurs when the acceptor type, Al ? Si, substitution is executed. The hole polaron in this structure localizes on three O atoms located near the Al impurity. Moreover, the Al impurity switch for either Mg or Si host atom somewhat increases the covalent character in the chemical bonding of the ilmenite mineral.

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References
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